Materials based on radically polymerizable N,O-functionalized acrylic acid hydroxamides

ABSTRACT

The present invention relates to a dental material comprising, relative to the total mass of the material:
         (a) 1 to 95 wt.-% of at least one polymerizable N,O-functionalized acrylic acid hydroxamide,   (b) 0 to 70 wt.-% diluent monomer,   (c) 0 to 70 wt.-%, cross-linker monomer,   (d) 0.1 to 5.0 wt.-% polymerization initiator   (e) 0 to 80 wt.-% filler,   (f) 0 to 70 wt.-% solvent, and   (g) 0 to 70 wt.-% adhesive monomer.

This application is a divisional application of U.S. application Ser.No. 11/898,338, filed Sep. 11, 2007, now U.S. Pat. No. 7,932,303, whichclaims priority pursuant to 35 U.S.C. §119, to European PatentApplication No. 07005396.2 filed Mar. 15, 2007, all of which areincorporated herein by reference.

FIELD

According to certain aspects, the present invention relates to radicallypolymerizable, N,O-functionalized acrylic acid hydroxamides ascross-linkers and/or adhesive monomers. According to additional aspects,the present invention also relates to dental materials, adhesives,coatings or composites comprising radically polymeriableN,O-functionalized acrylic acid hydroxamides as cross-linkers and/oradhesive monomers.

BACKGROUND

In the discussion that follows, reference is made to certain structuresand/or methods. However, the following references should not beconstrued as an admission that these structures and/or methodsconstitute prior art. Applicant expressly reserves the right todemonstrate that such structures and/or methods do not qualify as priorart.

Amides of acrylic or methacrylic acid are known as comonomers for thepreparation of polymers for prostheses (GB-A-1 039 750) or dentureadhesives (DE-A-2 316 603, U.S. Pat. No. 3,926,870, U.S. Pat. No.5,011,868). Furthermore, selectively substituted acrylamides ormethacrylamides are suitable as effective adhesion components in dentaladhesives, which for example are the subject of U.S. Pat. No. 3,660,343or EP-A-0 394 792 or have been described by S. Kitoh et al (cf. J. Appl.Polym. Sci. 39 (1990) 103, J. Appl. Polym. Sci. 51 (1994) 2021).Finally, because of their improved hydrolysis stability compared withconventional dimethacrylate cross-linkers, multifunctional(meth)acrylamides are particularly suitable as cross-linkers foraqueous-acid enamel-dentine adhesives (cf. N. Moszner, F. Zeuner, J.Angermann, U. K. Fischer, V. Rheinberger, Macromol. Mater. Eng. 288(2003) 621; U.S. Pat. No. 6,953,832) and also for self-adhesivecomposites (cf. N. Moszner, U. K. Fischer, J. Angermann, V. Rheinberger,Dent. Mater. 22 (2006) 1157).

N-alkoxy-N-alkylamides, also called Weinreb amides, are intermediateproducts established in modern organic synthesis chemistry, e.g., forthe synthesis of sterically demanding ketones or as substrate forenantioselective Diels-Alder reactions (M. Mentzel, H. M. R. Hoffmann,J. prakt. Chem. 330 (1997) 517). Weinreb amides can be accessed easily,e.g., by acylation of N,O-dimethylhydroxylamine with the correspondingacid chloride. The Weinreb amides are also characterized by aconsiderable stability and can accordingly be purified by customarymethods, e.g., by crystallization, distillation or chromatography. Aboveall the N-methoxy-N-methyl acrylamide is known as polymerizableN,O-functionalized carboxylic acid hydroxamide (cf. U. K. Fischer, N.Moszner, F. Zeuner, V. Rheinberger, Tagungsband derGDCh-Fachgruppentagung Polymers & Coatings (conference booklet of theGerman Chemical Society), Sep. 24-26, 2006, Mainz, p. 82). On the otherhand, the use of polymerizable, N,O-functionalized acrylic acidhydroxamides for the preparation of dental materials is not described.

SUMMARY

According to certain aspects, the invention provides a material whichcan be very quickly cured by means of radical polymerization. Thus, incertain embodiments, a cross-linking material (composite or coating)and/or material adhering to a hard tooth substance (adhesive, compositeor coating) formed which can be particularly suitable for dentalpurposes.

According to further aspects of the invention, a material is providedwhich is characterized in that it contains at least a polymerizableN,O-functionalized acrylic acid hydroxamide of the general Formula (I)

in which

-   A is an n+m-valent linear or branched aliphatic C₁ to C₅₀ radical,    in which the carbon chain can be interrupted by O, S, —CO—O—, CO—NH,    O—CO—NH or NH—CO—NH, an n+m-valent aromatic C₆ to C₁₈ radical or an    n+m-valent cycloaliphatic or heterocyclic C₃ to C₁₈ radical, wherein    the radicals can carry one or more substituents,-   Y is not present, or is O, S, an ester, amide or urethane group,-   R¹ is hydrogen, an aliphatic C₁ to C₂₀ alkyl or C₃ to C₈ cycloalkyl    radical which can carry one or more substituents,-   R² is H or a C₁ to C₁₀ alkyl radical,-   R³ is not present or is a C₁ to C₁₆ alkylene radical which can be    interrupted by O,-   HG is not present, is —COOH, —P═O(OH)₂; —P═O(OH)(OR⁴); —O—P═O(OH)₂,    —SO₂OH or —O—P═O(OH)(OR⁴),-   R⁴ is a C₁ to C₁₅ alkyl radical, phenyl or benzyl radical and-   n is a number from 1 to 5 and-   m a number from 0 to 3.

The present invention also includes the use of an amide of the generalFormula (I) as a dental material or for the preparation of a dentalmaterial, i.e., of a material for use as a dental material.

As used herein, dental materials according to the invention includedental adhesives, a dental coating materials, a dental fillingmaterials, dental cements, an indirect or direct restorative for dentalinlays, dental onlays, dental veneering materials for crowns andbridges, dental materials for artificial teeth or other applications inprosthetic, preservative and preventive dentistry as finished articles,raw materials or components thereof.

DETAILED DESCRIPTION

Polymerizable N,O-functionalized acrylic acid hydroxamides of thegeneral Formula (I) represent monomers of different type and reactivitywhich, optionally in mixtures with other polymerizable components, bycopolymerization in the presence of suitable radical initiators,thermally or upon irradiance of light of the visible, UV or IR range,result in mechanically stable coatings or shaped bodies. The selectionand number of the polymerizable or functional groups allows adistinction to be made between different types of the polymerizableN,O-functionalized acrylic acid hydroxamides according to of the generalFormula (I):

-   n=1, m=0: monofunctional N,O-functionalized acrylamides,-   n=2-5, m=0: multifunctional N,O-functionalized acrylamides which can    be used as cross-linkers,-   n=1, m=1: monofunctional N,O-functionalized acrylamides which carry    an acid adhesion group,-   n=2-5, m=1: cross-linking, multifunctional N,O-functionalized    acrylamides which carry an acid adhesion group and-   n=2-5, m=2-3: cross-linking, multifunctional N,O-functionalized    acrylamides which possess several acid adhesion groups.

Thus, depending on the selection of the polymerizable N,O-functionalizedacrylic acid hydroxamides of the general Formula (I), materials withdifferent properties and different dental applications can be prepared.

Thus the multifunctional N,O-functionalized acrylic acid amides (n=2-5,m=0) are suitable as a cross-linker component particularly forcomposites or cements, wherein the cross-linking density or themechanical properties, such as elastic modulus, of the cured materialsincrease or improve with increasing functionality, i.e., with increasingn. The cross-linking density of such materials can also be reduced bycopolymerization with monofunctional N,O-functionalized acrylic acidamides (n=1, m=0).

Monofunctional, N,O-functionalized acrylamides which carry an acidadhesion group (n=1, m=1) can be used as adhesive monomers in thepreparation of adhesives. Through the selective addition ofmultifunctional, cross-linking N,O-functionalized acrylic acid amides tothese adhesives their rate of curing can be increased, wherein as aresult of the cross-linking the swellability of the adhesive coatdecreases and its strength increases.

Alternatively, above all the cross-linking, multifunctionalN,O-functionalized acrylic acid amides which carry an acid adhesiongroup (n=2-5, m=1) or even the cross-linking, multifunctionalN,O-functionalized acrylic acid amides which possess several acidadhesion groups (n=2-5, m=2-3) can be used for such rapidly curingadhesives.

Finally, the N,O-functionalized acrylic acid amides which carry one ormore acid adhesion groups and contain one or more N,O-functionalizedacrylic acid amide radicals can be used as a component of dentalcomposites, cements or coating materials. The corresponding materialsthen show self-adhesive properties.

The N,O-functionalized acrylamides of the general Formula (I) can beprepared by reaction of N,O-functionalized amines with acrylic acidhalides (CH₂═CR²COX, X=Cl or Br) using the methods known from organicchemistry for forming amide bonds (cf. Methoden der Organischen Chemie,HOUBEN-WEYL Vol. E5 1985, Georg Thieme Verlag p. 941 ff.):

The corresponding acid chlorides are preferably used in the presence ofequimolar quantities of auxiliary base, e.g., triethylamine or pyridine(in the following specific example R¹═CH₃, R²═H, A=C₆H₁₂, n=2; Y, R³ andHG are dispensed with.):

The secondary N-methoxyamines used here can be prepared via the2-nitrobenzenesulfonyl protective group analogously to the synthesis ofsecondary amines (cf. W. Kurosawa, T. Kan, T. Fukuyama, Org. Synth. 79(2002) 186). For example, the above 1,6-Di(N-methoxyamino)hexane can beobtained by the reaction of 1,6-dibromohexane withN-methoxy-2-nitrobenzenesulfamide and deprotection of the formedsulfamide with thiophenol (Ph-SH). The requiredmethoxy-2-nitrobenzenesulfamide can be synthesized easily by reactingO-methylhydroxylamine hydrochloride with 2-nitrobenzene sulfonylchloride:

Analogously other hydroxylamine derivatives of the general structureR¹—O—NH₂ can also be reacted. These hydroxylamine derivatives can beprepared by reacting the corresponding alcohols R¹—OH withtriphenylphosphine ((Ph)₃P), N-hydroxyphthalimide anddiisopropyl-azodicarboxylate (DIAD) and then hydrazinolysis of theformed phthalimide derivative (cf. E. Grochowski, J. Jurczak, Synthesis1976, 682; S. Su, J. R. Giguere, S. E. Schaus, J. A. Porco, Tetrahedron60 (2004) 8645):

If N,O-functionalized acrylamides of the general Formula (I) areprepared which carry one or more acid groups HG, thus likewise the useof the correspondingly usual protective group technique is necessary.Accordingly it is advantageous not to split off the acid function fromthe protective groups until the last synthesis step. For example,N,O-functionalized acrylamides with a phosphonic acid function (e.g.,R¹═CH₃, R²═H, HG=—P═O(OH)₂, n and m=1, A=alkylene, R³ and Y are notpresent) can be prepared such that initially a α,ω-halogenalkylenephosphonic acid di-tert-butylester (tert-butyl group=protective group,X=halogen such as Cl or Br) is reacted withN-methoxy-2-nitrobenzenesulfamide. By deprotecting the formed sulfamideand then reacting the N-methoxyamino group with acrylic acid chloridethe N,O-functionalized acrylic acid amide forms, the phosphonic acidgroup of which is released after splitting off the two tert-butylprotective groups with trifluoroacetic acid (TFA).

In one embodiment of the invention the one or more substituents at theradical A are selected from the group comprising C₁ to C₅ alkyl groups,Cl, Br and OH, in particular C₁ to C₃ alkyl groups and OH. The one ormore substituents at the radical R¹ are selected from the groupcomprising Cl, Br and OH.

A material according to the invention based on an N,O-functionalizedacrylic acid amide of the general Formula (I) is one in which

-   A is an n+m-valent linear or branched aliphatic C₁ to C₃₀ radical,    e.g., a C₁ to C₁₅ radical or a C₁ to C₁₀ radical, in which the    carbon chain can be interrupted by O, —OO—O— or O—CO—NH, an    n+m-valent aromatic C₆ to C₁₀ radical, or an n+m-valent    cycloaliphatic C₃ to C₁₈ radical, wherein the radicals can carry one    or more substituents,-   Y is not present, or is O, an ester or urethane group,-   R¹ is an aliphatic C₁ to C₈ alkyl or cycloalkyl radical, e.g., a C₁    to C₄ alkyl or cyclohexyl radical,-   R² is H or CH₃,-   R³ is not present or is a C₁ to C₁₂ alkylene radical which can be    interrupted by O, e.g., a C₆ to C₁₂ alkylene radical,-   HG is not present, is —COOH, —P═O(OH)₂, —O—P═O(OH)₂, —SO₂OH or    —O—P═O(OH)(OR⁴),-   R⁴ is a C₁ to C₄ alkyl radical, e.g., methyl, ethyl, propyl or    butyl,-   n is a number from 1 to 3 and-   m a number from 0 to 2.

A further material according to the invention based on anN,O-functionalized acrylic acid amide of the general Formula (I) is onein which

-   A is an n+m-valent linear or branched aliphatic C₁ to C₁₂ radical,    e.g., C₁ to C₁₀ alkyl or C₁ to C₁₂ alkylene, an n+m-valent    cycloaliphatic C₆ to C₁₂ radical or an n+m-valent aromatic C₆ to C₁₀    radical,-   Y is not present or is an ester group,-   R¹ is a C₁ to C₄ alkyl,-   R² is H or CH₃,-   R³ is not present or is a C₄ to C₈ alkylene radical which can be    interrupted by O,-   HG is not present, or is —COOH, —P═O(OH)₂, —OP═O(OH)₂,    —OP═O(OH)(OC₂H₅) or —SO₂OH,-   n is 1, 2 or 3 and-   m is 0 or 1.

One particular material according to the invention based on anN,O-functionalized acrylic acid amide of the general Formula (I) is onein which

-   A is an n+m-valent linear or branched aliphatic C₁ to C₅ radical    such as ethyl, propyl, butyl, ethylene, propylene, butylene,    pentylene or pentanetriyl, an n+m-valent cycloaliphatic C₆ radical    such as cyclohexyl, cyclohexylene, cyclohexantriyl, or an n+m-valent    aromatic C₆ radical such as phenyl or benzenetriyl,-   Y is not present or is —COO—,-   R¹ is methyl, ethyl or propyl,-   R² is H or CH₃,-   R³ is not present or is pentylene,-   HG is dispensed with, is —COOH, —P═O(OH)₂, —OP═O(OH)₂,    —OP═O(OH)(OC₂H₅) or —SO₂OH,-   n is 1, 2 or 3 and-   m is 0 or 1.

A N,O-functionalized acrylic acid amide of the general Formula (I)according to one embodiment of the invention, A can mean unsubstitutedC₆ alkylene, R¹ methyl, R²H and n=2, wherein m=0. Alternatively A canpreferably mean unsubstituted C₁₀ alkylene, R¹ methyl, R²H, n and meach=1 and HG —OP═O(OH)₂, wherein the radicals Y and R³ are not present.

Specific examples of the N,O-functionalized acrylic acid amides of thegeneral Formula (I) according to the invention, include, among others:

To prepare materials according to the invention, the N,O-functionalizedacrylic acid amides alone, their mixtures with one another or theirmixtures with other diluent monomers or cross-linker monomers are curedby radical polymerization. Before polymerization, in addition to theinitiator, possibly suitable solvents or further additives, such asfillers, stabilizers or other adhesive monomers, can be added.

Suitable radically polymerizable diluent monomers mono(meth)acrylamidesand/or mono(meth)acrylates, e.g., acrylamide, methacrylamide,N-ethylacrylamide, methyl, ethyl, butyl, benzyl, furfuryl orphenyl(meth)acrylate. As further cross-linker monomers, knownmultifunctional acrylates or methacrylates, such as e.g.,bisphenol-A-di(meth)acrylate, Bis-GMA (an addition product ofmethacrylic acid and bisphenol-A-diglycidylether), UDMA (an additionproduct of 2-hydroxyethyl methacrylate and2,2,4-hexamethylenediisocyanate), di-, tri- or tetraethylene glycoldi(meth)acrylate, decanediol di(meth)acrylate, trimethylene propanetri(meth)acrylate, pentaerythritol tetra(meth)acrylate and butanedioldi(meth)acrylate, 1,10-decanediol di(meth)acrylate or 1,12-dodecanedioldi(meth)acrylate, can be used.

The compositions based on N,O-functionalized acrylamides are cured aftersuitable initiators have been added by thermal, photochemical orredox-induced radical polymerization. Examples of thermal initiators arethe known peroxides, such as, e.g., dibenzoyl peroxides, dilaurylperoxides, tert-butylperoctoate or tert-butylperbenzoate and furtherazobisisobutyroethyl ester, azobisisobutyronitrile,azobis-(2-methylpropionamidine)dihydrochloride, benzopinacol or2,2-dimethyl benzopinacol.

Examples of suitable photoinitiators are dibenzoyl diethyl germanium ordibenzoyl dimethyl germanium, benzophenone, benzoin and theirderivatives or α-diketones or their derivatives such as9,10-phenanthraquinone, diacetyl or 4,4-dichlorobenzene. Particularly,camphorquinone and 2,2-dimethoxy-2-phenyl-acetophenone and moreparticularly α-diketones in combination with amines as a reductant, suchas e.g., 4-(N,N-dimethylamino)-benzoic acid ester,N,N-dimethylaminoethyl methacrylate, N,N-dimethyl-sym.-xylidine ortriethanolamine are used. In addition, acylphosphines, such as e.g.,2,4,6-trimethylbenzoyldiphenyl or bis(2,6-dichlorobenzoyl)-4-N-propylphenyl phosphinic oxide are also particularly suitable.

Redox-initiator combinations, such as e.g., combinations of benzoyl orlauryl peroxide with N,N-dimethyl-sym.-xylidine orN,N-dimethyl-p-toluidine, are used as initiators for a polymerizationcarried out at room temperature.

The N,O-functionalized acrylic acid amide cross-linkers are particularlysuitable as a cross-linking component of solutions of known stronglyacidic adhesive monomers. These include phosphoric acid estermethacrylates, such as e.g., 2-(methacryloyloxy)ethyl dihydrogenphosphate, di-[2-(methacryloyloxy)ethyl]hydrogen phosphate ordipentaerythritol pentamethacryloyloxy-dihydrogen phosphate (cf. N.Nakabayashi, P. D. Pashley, Hybridization of dental hard tissues,Quintess. Publ. Tokyo etc. 1998, 9 ff), and hydrolysis-stableacrylphosphonic acids, such as, e.g.2-[3-(dihydroxyphosphoryl)-oxa-propyl]acrylic acid ethyl ester or1,2-bis[1-dihydroxyphosphoryl)-1-[2-methylene-3-ylpropanic acid ethylester)oxy]methyl]-benzene, which are described in DE-A-197 46 708, areparticularly suitable.

Above all polar solvents, such as water, ethanol, acetone, acetonitrileor mixtures of these solvents can be used as solvents for theN,O-functionalized acrylic acid amides.

Optionally, the compositions according to the invention can containfurther additives, such as colorants (pigments or dyestuffs),stabilizers, aromatics, microbiocidal active ingredients, plasticizersor UV absorbers.

Furthermore the compositions according to the invention can be filledwith inorganic particles or fibres to improve the mechanical properties.Preferred inorganic particulate fillers are amorphous sphericalmaterials based on oxides, such as ZrO₂ and TiO₂ or mixed oxides ofSiO₂, ZrO₂ and/or TiO₂, nanoparticulate or microfine fillers such aspyrogenic silicic acid or precipitation silicic acid and macro- ormicrofillers such as quartz, glass ceramic or glass powder with anaverage particle size of 0.01 to 5 μm and x-ray opaque fillers, such asytterbium trifluoride.

A composition according to the invention may contain, in each caserelative to the total mass of the material:

-   -   (a) 1 to 95 wt.-% acrylamide of the general Formula (I),    -   (b) 0 to 70 wt.-% diluent monomer,    -   (c) 0 to 70 wt.-% cross-linker monomer,    -   (d) 0.1 to 5.0 wt.-% polymerization initiator    -   (e) 0 to 80 wt.-% filler,    -   (f) 0 to 70 wt.-% solvent, and    -   (g) 0 to 70 wt.-% adhesive monomer.

By diluent monomer and cross-linker monomer are meant monomers which donot fall under Formula (I). By adhesive monomer are meant monomers whichhave one or more acid adhesion groups and fall under the Formula (I) ornot.

A further composition according to the invention contains, in each caserelative to the total mass of the material:

-   -   (a) 5 to 70 wt.-% acrylamide of the general Formula (I),    -   (b) 0 to 40 wt.-% diluent monomer,    -   (c) 0 to 40 wt.-% cross-linker monomer,    -   (d) 0.2 to 2.0 wt.-% polymerization initiator    -   (e) 0 to 50 wt.-% filler,    -   (f) 0 to 50 wt.-% solvent, and    -   (g) 0 to 50 wt.-% adhesive monomer.

A composition according to the invention usable as dental adhesivecontains, in each case relative to the total mass of the material:

-   -   (a) 5 to 40 wt.-%, in particular 10 to 40 wt.-% acrylamide of        the general Formula (I),    -   (b) 0 to 40 wt.-% diluent monomer,    -   (c) 0 to 70 wt.-%, in particular 50 to 70 wt.-% cross-linker        monomer, and    -   (d) 0.2 to 2.0 wt.-% polymerization initiator,    -   (e) 2 to 50 wt.-%, in particular 20 to 50 wt.-% solvent,    -   (f) 5 to 40 wt.-%, in particular 10 to 40 wt.-% adhesive        monomer,    -   (g) 0 to 20 wt.-% nanofiller (filler with a primary particle        size of <50 nm).

A composition according to the invention usable as dental cementcontains, in each case relative to the total mass of the material:

-   -   (a) 5 to 20 wt.-% acrylamide of the general Formula (I),    -   (b) 0 to 20 wt.-% diluent monomer,    -   (c) 0 to 20 wt.-% cross-linker monomer,    -   (d) 0.2 to 2.0 wt.-% polymerization initiator,    -   (e) 5 to 60 wt.-% filler, and    -   (f) 2 to 20 wt.-% adhesive monomer.

A composition according to the invention usable as dental fillingmaterial contains, in each case relative to the total mass of thematerial:

-   -   (a) 5 to 20 wt.-% acrylamide of the general Formula (I),    -   (b) 0 to 30 wt.-% diluent monomer,    -   (c) 0 to 30 wt.-% cross-linker monomer,    -   (d) 0.2 to 2.0 wt.-% polymerization initiator, and    -   (e) 10 to 80 wt.-%, in particular 50 to 80 wt.-% solvent.

A composition according to the invention usable as dental coatingmaterial contains, in each case relative to the total mass of thematerial:

-   -   (a) 5 to 40 wt.-% acrylamide of the general Formula (I),    -   (b) 0 to 50 wt.-% diluent monomer,    -   (c) 0 to 50 wt.-% cross-linker monomer,    -   (d) 0.2 to 2.0 wt.-% polymerization initiator,    -   (e) 2 to 50 wt.-% solvent, and    -   (f) 0 to 20 wt.-% nanofiller (filler with a primary particle        size of <50 nm).

The invention is described in further detail below with reference to thefollowing illustrative, non-limiting examples.

Example 1 Synthesis of 1,6-bis(N-acryloyl-N-methoxyamino) hexane 1^(st)stage: N-methoxy-2-nitrobenzenesulfonamide (1)

2-nitrobenzene sulfonyl chloride (28.8 g, 130 mmol) was added within 30min to a solution of O-methylhydroxylamine hydrochloride (11.7 g, 141mmol) in pyridine (100 ml) accompanied by stirring and water cooling.After the addition the mixture was stirred for a further 30 min at roomtemperature (RT), mixed with ice (200-300 g) and acidified withconcentrated HCl to pH 2-3. The still-cold suspension was sucked out,the precipitate carefully washed with ice water and dried. 26.4 g (87%)of the sulfamide 1 was obtained as a yellowish solid with a meltingpoint of 133-136° C. ¹H-NMR (DMSO-D₆, 300 MHz): δ=3.67 (s, 3H),7.92-8.06 (m, 4H), 11.05 (s, 1H) ppm.

2^(nd) Stage: N,N′-dimethoxy-2,2′-dinitrohexamethylenedi(benzenesulfamide) (2)

A mixture of the sulfamide 1 (24.1 g, 104 mmol), 1,6-dibromohexane (12.2g, 5.0 mmol) and K₂CO₃ (17.0 g, 123 mmol) in DMF (100 ml) was stirredintensively at 70-80° C. for 3 h, cooled and approximately 5 times thevolume of water added to it. After dilution with water the crude productprecipitated out as deposit. It was sucked off, washed with plenty ofwater and dissolved in CH₂Cl₂ (approx. 500 ml). The solution was driedover anhydrous MgSO₄ and concentrated under vacuum to approximately onequarter of the volume. Approximately the same volume of hexane was addedto the residue, sucked off after standing in the refrigerator for 1 h,washed with a 1:1 mixture of methylene chloride and hexane and dried.26.1 g (96%) of the sulfonamide 2 was obtained as an almost colourlesssolid with a melting point of 145-146° C. ¹H-NMR (DMSO-D₆, 300 MHz):δ=1.37 (m_(c), 4H), 1.59 (m_(c), 4H), 2.99 (t, J=7 Hz, 4H), 3.77 (s,6H), 7.86-7.92 (m, 2H), 7.97-8.02 (m, 6H) ppm.

3^(rd) stage: 1,6-di(N-methoxyamino)hexane (3)

A mixture of the sulfamide 2 (28.1 g, 51.4 mmol), K₂CO₃ (43 g, 312 mmol)and thiophenol (22.6 g, 206 mmol) in DMF (150 ml) was stirredintensively for 2-6 h at 40-45° C. (DC control). For working-up, themixture was diluted with approximately 2 times the volume of water andether. The cooled solution was very carefully acidified withconcentrated HCl (CO₂ formation, thiophenol) and the acid aqueous phasewas separated off. The organic phase was washed again with 5% HCl (2×100ml). The combined acid phases were washed with ether (2×100 ml), cooledwith ice water and very carefully made strongly alkaline with solid KOH(vigorous build-up of heat). The product was precipitated out as ayellow-orange oil. This was extracted with ether (3×50 ml), the solutiondried over K₂CO₃ and concentrated under vacuum. 8.48 g (89%) of thediamine 3 was obtained. For final purification this diamine wasdistilled under vacuum almost without losses, boiling point 95-97° C.(0.5 Torr). ¹H-NMR (CDCl₃, 300 MHz): δ=1.33 (m_(c), 4H), 1.47 (m_(c),4H), 2.87 (t, J=7 Hz, 4H), 3.50 (s, 6H), 5.49 (br. s, 2H) ppm.

4^(th) stage: 1,6-bis(N-acryloyl-N-methoxyamino)hexane (4)

Acrylic acid chloride (996 mg, 11 mmol) was added dropwise within 5 minto a stirred suspension of the bis-methoxyamine 3 (881 mg, 5 mmol),Na₂CO₃ (2.65 g, 25 mmol) and BHT (=2,6-tert-butyl-4-methylphenol) (10mg) in anhydrous diethylether (100 ml) accompanied by ice-cooling. Thereaction mixture was then left to heat up to room temperature andstirred for a further 16 h. After the bis-methoxyamine 3 was completelyconsumed, water (20 ml) was added, the organic phase separated off andthe aqueous phase extracted with diethyl ether (3×20 ml). The organicphases were combined, the solvent removed under vacuum and the crudeproduct purified using column chromatography (silica gel, eluentchloroform/ethyl acetate 3:1). 1.1 g (79%)1,6-bis(N-acryloyl-N-methoxyamino)hexane 4 was obtained. ¹H-NMR (300MHz, CDCl₃): δ=1.31-1.36 (m, 4H), 1.59-1.69 (m, 4H), 3.65 (t, J=7.2 Hz,4H), 3.68 (s, 6H), 5.74 (dd, J=10.3, 2.1 Hz, 2H), 6.41 (dd, J=17.1, 2.1Hz, 2H), 6.71 (dd, J=17.1, 10.3 Hz, 2H) ppm. ¹³C-NMR (75 MHz, CDCl₃):δ=26.4 (2CH₂), 26.9 (2CH₂), 44.9 (2CH₂), 62.1 (2CH₃), 126.2 (CH), 128.9(CH₂), 166.1 (2C) ppm.

Example 2 Synthesis of [10-(N-acryloyl-N-methoxyamino) decyl]phosphoricacid (5) 1^(st) stage: 10-hydroxydecyl-di-tert-butyl phosphate (6)

Anhydrous THF (400 ml) was added accompanied by stirring under nitrogento a mixture of 1,10-decanediol (34.9 g, 200 mmol) and sodium hydride(8.1 g of a 60% suspension in mineral oil, 200 mmol). The reactionmixture was heated for 18 h under reflux. After the addition ofdi-tert-butylchlorophosphate (27 g, 118 mmol), which according to theliterature (cf. H. Goldwhite, B. C) Saunders, J. Chem. Soc. 1957,2409-2412; T. Gajda, A. Zwierzak, Synthesis 1976, 243-244) wasobtainable in 2 stages from PCl₃ and tert-butanol, was heated for afurther 1.5 h under reflux and the solvent then removed under vacuum. Amixture of tert-butyl methyl ether (MTBE, 400 ml) and water (100 ml) wasadded to the residue. After separation of the organic phase this waswashed with a 10% NaCl solution and washed with saturated NaCl solution.It was then dried over anhydrous magnesium sulfate and the solventremoved. The residue was dissolved in some boiling MTBE. By adding 5times the quantity of pentane, non-reacted decanediol could becrystallized out. After filtration the crude product was purified usingcolumn chromatography (silica gel, eluent: Chloroform/MTBE 8:1 to 3:1).19.3 g (45%) 10-hydroxydecyl-di-tert-butyl phosphate 6 was obtained as acolourless, highly-viscous oil.

2^(nd) stage 10-(methanesulfonyloxy)decyl-di-tert-butyl phosphate (7)

Freshly distilled mesylchloride (4.5 g, 39.3 mmol) was added dropwiseaccompanied by stirring over a period of 1 h to a solution of10-hydroxydecyl-di-tert-butyl phosphate 6 (12.6 g, 34.4 mmol),triethylamine (5.5 ml, 39.5 mmol) and DMAP (=4-(dimethylamino)-pyridine)(220 mg, 1.8 mmol) in anhydrous methylene chloride (35 ml) such that thetemperature of the reaction mixture remained between −5 and 0° C. Thiswas then heated to room temperature, stirred for a further 1 h, thesolvent removed under reduced pressure and a mixture of MTBE(=tert-butyl methyl ether) (100 ml) and water (50 ml) was added to theresidue. This mixture was set to pH˜5 with 10% H₂SO₄. The aqueous phasewas extracted with MTBE (3×30 ml). The combined organic phases werewashed with water (30 ml) and saturated NaCl solution (2×50 ml) anddried over anhydrous magnesium sulfate. The removal by distillation ofthe solvent resulted in 15.2 g10-(methanesulfonyloxy)decyl-di-tert-butyl phosphate 7 as a slightlyyellowish oil. ¹H-NMR (CDCl₃, 250 MHz): δ=1.25-1.45 (m, 12H), 1.47 (s,18H), 1.58-1.80 (m, 4H), 3.00 (s, 3H), 3.93 (q, J=6.6 Hz, 2H), 4.22 (t,J=6.6 Hz, 2H) ppm.

3^(rd) stage: 10-methoxyaminodecyl-di-tert-butyl phosphate (8)

The mesylate 7 (15.2 g, 34.2) in acetone (5 ml) was added accompanied bystirring to a suspension of anhydrous NaI (6.85 g, 45.7 mmol) in dryacetone (30 ml). The mixture was stirred for 24 h at room temperature.The solvent was then removed and the residue was dispersed in a mixtureof MTBE (100 ml), water (50 ml) and 100 mg Na₂S₂O₄. The organic phasewas separated off and the aqueous phase was extracted with MTBE (3×30ml). The combined organic phases were washed with water (30 ml) andsaturated NaCl solution (2×50 ml) and dried over anhydrous magnesiumsulfate. The solvent was then removed. The thus-obtained slightlyyellowish liquid iodide (16.3 g, 34 mmol) (¹H-NMR (CDCl₃, 250 MHz):δ=1.25-1.46 (m, 12H), 1.48 (s, 18H), 1.64 (tt, J=6.8, 6.6 Hz, 2H), 1.81(tt, J=7.0, 6.8 Hz, 2H), 3.18 (t, J=7.0 Hz, 2H), 3.93 (q, J=6.6 Hz, 2H)ppm) was dissolved in anhydrous THF (14 ml) and added to a suspension ofmethoxyamine (14.0 g, 297 mmol) and NaH (1.36 g of a 60% suspension inmineral oil, 34 mmol) in THF (20 ml) accompanied by stirring. Thereaction mixture was heated for 16 h under reflux. After evaporating offthe solvent under vacuum dry hexane was added to the residue and thiswas then stirred for 2 h. Filtration through a thin sheet of Celite®then took place and the solvent was removed. The crude product (12.4 g)was purified by flash chromatography (silica gel (450 ml), eluentchloroform/MTBE/ethyl acetate, 4:1:0 to 4:1:1), wherein 8.58 g (64%) of10-methoxyaminodecyl-di-tert-butyl phosphate 8 was obtained. ¹H-NMR(CDCl₃, 300 MHz): δ=1.22-1.40 (m, 12H), 1.47 (s, 18H), 1.45-1.55 (m,2H), 1.64 (tt, J=6.8, 6.6 Hz, 2H), 2.90 (t, J=7.3 Hz, 2H), 3.53 (s, 3H),3.93 (q, J=6.6 Hz, 2H), 5.53 (bs, 1H) ppm. ¹³C-NMR (CDCl₃, 75.5 MHz):δ=25.6 (CH₂), 27.2 (CH₂), 27.3 (CH₂), 29.2 (CH₂), 29.4 (CH₂), 29.5(CH₂), 29.8 (CH₃), 29.9 (CH₃), 30.2 (CH₂), 30.3 (CH₂), 51.9 (CH₂), 62.8(CH₃), 66.8 (CH₂), 66.9 (CH₂), 81.8 (C), 81.9 (C) ppm.

4^(th) stage: [10-(N-acryloyl-N-methoxyamino)decyl]phosphoric aciddi-tert-butylester (9)

A solution of acrylic acid chloride (996 mg, 11 mmol) in CH₂Cl₂ (4 ml)was added dropwise accompanied by stirring over a period of 1 h to asolution of methoxyamine 8 (3.96 g, 10 mmol), triethylamine (1.53 ml, 11mmol), DMAP (122 mg, 1 mmol) and BHT (10 mg) in CH₂Cl₂ (16 ml) such thatthe temperature of the reaction mixture remained between −5 and 0° C.After heating to room temperature, stirring took place for 16 h and thenthe solvent was distilled off under vacuum. A mixture of (50 ml) andwater (25 ml) was added to the residue obtained. This mixture was set topH ˜5 with 10% H₂SO₄. After separating off the organic phase the aqueousphase was extracted with MTBE (3×20 ml). The combined organic phaseswere washed with water (20 ml) and saturated NaCl solution (2×25 ml) anddried over anhydrous magnesium sulfate. After the removal bydistillation of the solvent an oil was obtained which was purified byflash chromatography (silica gel (100 ml), eluent chloroform/MTBE 6:1 to3:1), wherein 3.19 g (71%)[10-(N-acryloyl-N-methoxyamino)decyl]phosphoric acid di-tert-butyl ester9 was obtained as a weakly yellowish oil. ¹H-NMR (CDCl₃, 250 MHz):δ=1.22-1.39 (m, 12H), 1.47 (s, 18H), 1.58-1.69 (m, 4H), 3.65 (t, J=7.4Hz, 2H), 3.69 (s, 3H), 3.93 (q, J=6.6 Hz, 2H), 5.74 (dd, J=10.3, 2.0 Hz,1H), 6.42 (dd, J=17.1, 2.0 Hz, 1H), 6.72 (dd, J=17.1, 10.3 Hz, 1H) ppm.¹³C-NMR (CDCl₃, 75,5 MHz): δ=25.6 (CH₂), 26.7 (CH₂), 27.0 (CH₂), 29.1(CH₂), 29.2 (CH₂), 29.3 (CH₂), 29.4 (CH₂), 29.8 (CH₃), 29.9 (CH₃), 30.2(CH₂), 30.3 (CH₂), 62.1 (CH₃), 66.8 (CH₂), 66.9 (CH₂), 81.8 (C), 81.9(C), 126.2 (CH), 128.9 (CH₂), 166.0 (C) ppm.

5^(th) stage: [10-(N-acryloyl-N-methoxyamino)decyl]phosphoric acid (10)

[10-(N-acryloyl-N-methoxyamino)decyl]phosphoric acid di-tert-butyl ester9 (4.5 g, 10 mmol) was dissolved in tetrachlorocarbon (20 ml) and wasadded to this trifluoroacetic acid (3.07 g, 26.9 mmol). The reactionmixture was heated on the rotary evaporator (600-630 mbar) for 1 h to50° C. and the pressure then reduced over 1 h to 5 mbar. The residue wasthen dried in the fine vacuum (approx. 0.03 mbar) until weight wasconstant, wherein 2.84 g (84%)[10-(N-acryloyl-N-methoxyamino)decyl]phosphoric acid 10 was obtained asa yellowish oil. ¹H-NMR (CDCl₃, 300 MHz): δ=1.28-1.37 (m, 12H),1.64-1.67 (m, 4H), 3.67-3.71 (m, 5H), 4.01 (q, 2H), 5.83 (dd, 1H), 6.42(dd, 1H), 6.46 (m, 1H), 11.56 (s, 2H) ppm. ³¹P-NMR (DMSO-d₆, 162 MHz):δ=2.58 ppm.

Example 3 Radical polymerization of the bis(meth)acrylamide 4

In Schlenk flasks, solutions of 30%1,6-bis(N-acryloyl-N-methoxyamino)hexane 4 from example 1 or 30%glycerol dimethacrylate were prepared as a comparative example and 1mass-% 2,2′-azobis-(isobutyronitrile) (initiator) in chlorobenzene anddegassed by passing through argon. The polymerization batches were thenheated to 56° C. in a constant-temperature chamber. The time taken for athree-dimensional stable gel to form was measured as gelling time.

Cross-linker Gelling time 1,6-bis(N-acryloyl-N-methoxyamino) hexane 4 80s Glycerine dimethacrylate (comparative example)  7 min

The example demonstrates the high reactivity of the grapevinecross-linkers in radical polymerization compared with commercialdimethacrylates.

Example 4 [10-(N-acryloyl-N-methoxyamino)decyl]phosphoric acid 10Containing Dentine Adhesive from Example 3

To investigate the dentine adhesion on bovine tooth dentine an adhesiveof the following composition (figures in wt.-%) was prepared:

Strongly acid adhesive monomer 10^(a)): 11.1% Glycerine dimethacrylate:11.0% 2-hydroxyethyl methacrylate: 20.0% Ethanol: 24.0% Bis-GMA: 33.1%Photoinitiator: 0.8%^(a))[10-(N-acryloyl-N-methoxyamino)decyl]phosphoric acid

Bovine teeth were embedded in a plastic cylinder such that the dentineand the plastic were on one level. After 15 s etching with 37%phosphoric acid was followed by thorough washing with water. Thedentinal tubules were opened by the acid etching. A layer of adhesive ofthe above composition was then applied with a microbrush, the solventremoved by operating the airbrush for a short time and lit for 40 s witha halogen lamp (Astralis 7, Ivoclar Vivadent AG). A composite cylinderof Tetric® Ceram (Ivoclar Vivadent AG) was then polymerized onto theadhesive layer in two layers each of 1-2 mm by 40 s lighting in eachcase with the halogen lamp Astralis 7. The test pieces were then storedin water for 24 h at 37° C. and the shearing adhesive strength measuredat 17.0 MPa, which represents a very high coefficient of dentineadhesion for a non-optimized adhesive composition.

Example 5 [10-(N-acryloyl-N-methoxyamino)decyl]phosphoric acid 10Containing Self-Adhesive Composite from Example 3

To investigate the dentine adhesion on bovine tooth dentine a compositeof the following composition (figures in wt.-%) was prepared:

Strongly acid adhesive monomer 10^(a)): 3.0% UDMA 5.7%2-acetoacetoxyethyl methacrylate: 3.0% Bis-GMA: 8.0%Photoinitiator^(b)): 0.3% Fillers^(c)): 80.0%^(a))[10-(N-acryloyl-N-methoxyamino)decyl]phosphoric acid ^(b))Mixtureof 0.1% camphorquinone and 0.2% 4-dimethylaminobenzoic acid ethyl ester^(c))Mixture of 39 wt.-% silanized Ba—Al-silicate glass filler and 41wt.-% isofiller.

Embedded bovine teeth were used analogously to example 4. The dentinesurface was firstly finely-(P120) then very finely-sanded (P600). A thinlayer of the above-described composite was directly applied to thisdentine surface and a composite cylinder of Tetric® Ceram (IvoclarVivadent AG) with a diameter of 4 mm was then pressed onto this. Then itwas lit from all sides 4×20 s with the Astralis 7 halogen lamp. The testpieces were then stored in water for 24 h at 37° C. and the shearingadhesive strength measured at 7.2 MPa, which represents an excellentvalue for self-adhesion of a composite.

All numbers expressing quantities or parameters used in thespecification are to be understood as additionally being modified in allinstances by the term “about”. Notwithstanding that the numerical rangesand parameters set forth, the broad scope of the subject matterpresented herein are approximations, the numerical values set forth areindicated as precisely as possible. For example, any numerical value mayinherently contain certain errors, evidenced by the standard deviationassociated with their respective measurement techniques, or round-offerrors and inaccuracies.

Although the present invention has been described in connection withpreferred embodiments thereof, it will be appreciated by those skilledin the art that additions, deletions, modifications, and substitutionsnot specifically described may be made without department from thespirit and scope of the invention as defined in the appended claims.

What is claimed is:
 1. A dental material comprising (a) 1 to 95 wt. % ofat least one polymerizable N,O functionalized acrylic acid hydroxamideof the general Formula (I):

in which A is an n+m valent linear or branched aliphatic C₁ to C₅₀radical, in which the carbon chain can be interrupted by O, S, —CO—O—,CO—NH, O—CO—NH or NH—CO—NH, an n+m valent aromatic C₆ to C₁₈ radical oran n+m valent cycloaliphatic or heterocyclic C₃ to C₁₈ radical, whereinthe radicals can carry one or more substituents, Y is not present, or isO, S, an ester, amide or urethane group, R¹ is hydrogen, an aliphatic C₁to C₂₀ alkyl or C₃ to C₈ cycloalkyl radical which can carry one or moresubstituents, R² is H or a C₁ to C₁₀ alkyl radical, R³ is not present oris a C₁ to C₁₆ alkylene radical which can be interrupted by O, HG is notpresent, or is —COOH, —P═O(OH)₂; —P═O(OH)(OR⁴); —O—P═O(OH)₂, —SO₂OH or—O—P═O(OH)(OR⁴), R⁴ is a C₁ to C₁₅ alkyl radical, phenyl or benzylradical, n is a number from 2-5 and m is 0, (b) 0 to 70 wt. % diluentmonomer, (c) 0 to 70 wt. %, cross-linker monomer, (d) 0.1 to 5.0 wt. %polymerization initiator and (e) 0 to 80 wt. % filler, (f) 0 to 70 wt. %solvent, and (g) 0 to 70 wt. % adhesive monomer.
 2. A dental materialcomprising Formula (I):

in which A is an n+m valent linear or branched aliphatic C₁ to C₅₀radical, in which the carbon chain can be interrupted by O, S, —CO—O—,CO—NH, O—CO—NH or NH—CO—NH, an n+m valent aromatic C₆ to C₁₈ radical oran n+m valent cycloaliphatic or heterocyclic C₃ to C₁₈ radical, whereinthe radicals can carry one or more substituents, Y is not present, or isO, S, an ester, amide or urethane group, R¹ is hydrogen, an aliphatic C₁to C₂₀ alkyl or C₃ to C₈ cycloalkyl radical which can carry one or moresubstituents, R² is H or a C₁ to C₁₀ alkyl radical, R³ is not present oris a C₁ to C₁₆ alkylene radical which can be interrupted by O, HG is notpresent, or is —COOH, —P═O(OH)₂; —P═O(OH)(OR⁴); —O—P═O(OH)₂, —SO₂OH or—O—P═O(OH)(OR⁴), R⁴ is a C₁ to C₁₅ alkyl radical, phenyl or benzylradical, n is a number from 2-5 and m is 0, (b) 0 to 70 wt. % diluentmonomer, (c) 0 to 70 wt. %, cross-linker monomer, (d) 0.1 to 5.0 wt. %polymerization initiator and (e) 0 to 80 wt. % filler, (f) 0 to 70 wt. %solvent, and (g) 0 to 70 wt. % adhesive monomer.
 3. A dental materialcomprising Formula (I):

in which A is an n+m valent linear or branched aliphatic C₁ to C₅₀radical, in which the carbon chain can be interrupted by O, S, —CO—O—,CO—NH, O—CO—NH or NH—CO—NH, an n+m valent aromatic C₆ to C₁₈ radical oran n+m valent cycloaliphatic or heterocyclic C₃ to C₁₈ radical, whereinthe radicals can carry one or more substituents, Y is not present, or isO, S, an ester, amide or urethane group, R¹ is hydrogen, an aliphatic C₁to C₂₀ alkyl or C₃ to C₈ cycloalkyl radical which can carry one or moresubstituents, R² is H or a C₁ to C₁₀ alkyl radical, R³ is not present oris a C₁ to C₁₆ alkylene radical which can be interrupted by O, HG is notpresent, or is —COOH, —P═O(OH)₂; —P═O(OH)(OR⁴); —O—P═O(OH)₂, —SO₂OH or—O—P═O(OH)(OR⁴), R⁴ is a C₁ to C₁₅ alkyl radical, phenyl or benzylradical, n is a number from 2-5 and m is a number from 2-3, (b) 0 to 70wt. % diluent monomer, (c) 0 to 70 wt. %, cross-linker monomer, (d) 0.1to 5.0 wt. % polymerization initiator and (e) 0 to 80 wt. % filler, (f)0 to 70 wt. % solvent, and (g) 0 to 70 wt. % adhesive monomer.
 4. Adental adhesive comprising: (a) 5 to 40 wt.-% acrylamide of the generalFormula (I):

in which A is an n+m valent linear or branched aliphatic C₁ to C₅₀radical, in which the carbon chain can be interrupted by O, S, —CO—O—,CO—NH, O—CO—NH or NH—CO—NH, an n+m valent aromatic C₆ to C₁₈ radical oran n+m valent cycloaliphatic or heterocyclic C₃ to C₁₈ radical, whereinthe radicals can carry one or more substituents, Y is not present, or isO, S, an ester, amide or urethane group, R¹ is hydrogen, an aliphatic C₁to C₂₀ alkyl or C₃ to C₈ cycloalkyl radical which can carry one or moresubstituents, R² is H or a C₁ to C₁₀ alkyl radical, R³ is not present oris a C₁ to C₁₆ alkylene radical which can be interrupted by O, HG is notpresent, or is —COOH, —P═O(OH)₂; —P═O(OH)(OR⁴); —O—P═O(OH)₂, —SO₂OH or—O—P═O(OH)(OR⁴), R⁴ is a C₁ to C₁₅ alkyl radical, phenyl or benzylradical, n is a number from 1-5 and m is a number from 0-3, (b) 0 to 40wt.-% diluent monomer, (c) 0 to 70 wt.-% cross-linker monomer, (d) 0.2to 2.0 wt.-% polymerization initiator, (e) 2 to 50 wt.-% solvent, (f) 5to 40 wt.-% adhesive monomer, and (g) 0 to 20 wt.-% nanofiller (fillerwith a primary particle size of <50 nm).
 5. A dental cement comprising:(a) 5 to 20 wt.-% acrylamide of the general Formula (I): Formula (I):

in which A is an n+m valent linear or branched aliphatic C₁ to C₅₀radical, in which the carbon chain can be interrupted by O, S, —CO—O—,CO—NH, O—CO—NH or NH—CO—NH, an n+m valent aromatic C₆ to C₁₈ radical oran n+m valent cycloaliphatic or heterocyclic C₃ to C₁₈ radical, whereinthe radicals can carry one or more substituents, Y is not present, or isO, S, an ester, amide or urethane group, R¹ is hydrogen, an aliphatic C₁to C₂₀ alkyl or C₃ to C₈ cycloalkyl radical which can carry one or moresubstituents, R² is H or a C₁ to C₁₀ alkyl radical, R³ is not present oris a C₁ to C₁₆ alkylene radical which can be interrupted by O, HG is notpresent, or is —COOH, —P═O(OH)₂; —P═O(OH)(OR⁴); —O—P═O(OH)₂, —SO₂OH or—O—P═O(OH)(OR⁴), R⁴ is a C₁ to C₁₅ alkyl radical, phenyl or benzylradical, n is a number from 1-5 and m is a number from 0-3, (b) 0 to 20wt.-% diluent monomer, (c) 0 to 20 wt.-% cross-linker monomer, (d) 0.2to 2.0 wt.-% polymerization initiator, (e) 5 to 60 wt.-% filler, and (f)2 to 20 wt.-% adhesive monomer.
 6. A dental filling material comprising:(a) 5 to 20 wt.-% acrylamide of the general Formula (I):

in which A is an n+m valent linear or branched aliphatic C₁ to C₅₀radical, in which the carbon chain can be interrupted by O, S, —CO—O—,CO—NH, O—CO—NH or NH—CO—NH, an n+m valent aromatic C₆ to C₁₈ radical oran n+m valent cycloaliphatic or heterocyclic C₃ to C₁₈ radical, whereinthe radicals can carry one or more substituents, Y is not present, or isO, S, an ester, amide or urethane group, R¹ is hydrogen, an aliphatic C₁to C₂₀ alkyl or C₃ to C₈ cycloalkyl radical which can carry one or moresubstituents, R² is H or a C₁ to C₁₀ alkyl radical, R³ is not present oris a C₁ to C₁₆ alkylene radical which can be interrupted by O, HG is notpresent, or is —COOH, —P═O(OH)₂; —P═O(OH)(OR⁴); —O—P═O(OH)₂, —SO₂OH or—O—P═O(OH)(OR⁴), R⁴ is a C₁ to C₁₅ alkyl radical, phenyl or benzylradical, n is a number from 1-5 and m is a number from 0-3, (b) 0 to 30wt.-% diluent monomer, (c) 0 to 30 wt.-% cross-linker monomer, (d) 0.2to 2.0 wt.-% polymerization initiator, and (e) 10 to 80 wt.-% solvent.7. A dental coating material comprising: (a) 5 to 40 wt.-% acrylamide ofthe general Formula (I):

in which A is an n+m valent linear or branched aliphatic C₁ to C₅₀radical, in which the carbon chain can be interrupted by O, S, —CO—O—,CO—NH, O—CO—NH or NH—CO—NH, an n+m valent aromatic C₆ to C₁₈ radical oran n+m valent cycloaliphatic or heterocyclic C₃ to C₁₈ radical, whereinthe radicals can carry one or more substituents, Y is not present, or isO, S, an ester, amide or urethane group, R¹ is hydrogen, an aliphatic C₁to C₂₀ alkyl or C₃ to C₈ cycloalkyl radical which can carry one or moresubstituents, R² is H or a C₁ to C₁₀ alkyl radical, R³ is not present oris a C₁ to C₁₆ alkylene radical which can be interrupted by O, HG is notpresent, or is —COOH, —P═O(OH)₂; —P═O(OH)(OR⁴); —O—P═O(OH)₂, —SO₂OH or—O—P═O(OH)(OR⁴), R⁴ is a C₁ to C₁₅ alkyl radical, phenyl or benzylradical, n is a number from 1-5 and m is a number from 0-3, (b) 0 to 50wt.-% diluent monomer, (c) 0 to 50 wt.-% cross-linker monomer (d) 0.2 to2.0 wt.-% polymerization initiator, (e) 2 to 50 wt.-% solvent, and (f) 0to 20 wt.-% nanofiller (filler with a primary particle size of <50 nm).8. A dental material comprising (a) 1 to 95 wt. % of at least onepolymerizable N,O functionalized acrylic acid hydroxamide of the generalFormula (I):

in which A is an n+m valent linear or branched aliphatic C₁ to C₅₀radical, in which the carbon chain can be interrupted by O, S, —CO—O—,CO—NH, O—CO—NH or NH—CO—NH, an n+m valent aromatic C₆ to C₁₈ radical oran n+m valent cycloaliphatic or heterocyclic C₃ to C₁₈ radical, whereinthe radicals can carry one or more substituents, Y is not present, or isO, S, an ester, amide or urethane group, R¹ is hydrogen, an aliphatic C₁to C₂₀ alkyl or C₃ to C₈ cycloalkyl radical which can carry one or moresubstituents, R² is H or a C₁ to C₁₀ alkyl radical, R³ is not present oris a C₁ to C₁₆ alkylene radical which can be interrupted by O, HG is notpresent, or is —COOH, —P═O(OH)₂; —P═O(OH)(OR⁴); —O—P═O(OH)₂, —SO₂OH or—O—P═O(OH)(OR⁴), R⁴ is a C₁ to C₁₅ alkyl radical, phenyl or benzylradical, n is a number from 1 to 5 and m a number from 0 to 3, (b) 0 to70 wt. % diluent monomer, (c) 0 to 70 wt. %, cross-linker monomer, (d)0.1 to 5.0 wt. % polymerization initiator and (e) 0 to 80 wt. % filler,(f) 0 to 70 wt. % solvent, and (g) 0 to 70 wt. % adhesive monomer. 9.The method of making a dental material, the method comprising: (i)selecting a dental application material; (ii) providing (a) 1 to 95wt.-% of at least one polymerible N,O-functionalized acrylic acidhydroxamide of the general Formula (I):

in which A is an n+m valent linear or branched aliphatic C₁ to C₅₀radical, in which the carbon chain can be interrupted by O, S, —CO—O—,CO—NH, O—CO—NH or NH—CO—NH, an n+m valent aromatic C₆ to C₁₈ radical oran n+m valent cycloaliphatic or heterocyclic C₃ to C₁₈ radical, whereinthe radicals can carry one or more substituents, Y is not present, or isO, S, an ester, amide or urethane group, R¹ is hydrogen, an aliphatic C₁to C₂₀ alkyl or C₃ to C₈ cycloalkyl radical which can carry one or moresubstituents, R² is H, R³ is not present or is a C₁ to C₁₆ alkyleneradical which can be interrupted by O, HG is not present, or is —COOH,—P═O(OH)₂; —P═O(OH)(OR⁴); —O—P═O(OH)₂, —SO₂OH or —O—P═O(OH)(OR⁴), R⁴ isa C₁ to C₁₅ alkyl radical, phenyl or benzyl radical, n is a number from1 to 5 and m a number from 0 to 3, (b) 0 to 70 wt. % diluent monomer,(c) 0 to 70 wt. %, cross-linker monomer, (d) 0.1 to 5.0 wt. %polymerization initiator and (e) 0 to 80 wt. % filler, (f) 0 to 70 wt. %solvent, and (g) 0 to 70 wt. % adhesive monomer (iii) selecting thevalue of at least one of the variables n or m to influence one or moreof the functionality, cross-linking characteristics and adhesiveproperties of the dental material to tailor the properties of thematerial to optimize the performance thereof for the dental application;and (iv) compounding with other monomers, polymerization initiators,solvents or fillers to further tailor the properties of the material tooptimize the performance thereof for the dental application.
 10. Adental adhesive comprising: (a) 10 to 40 wt.-% acrylamide of the generalFormula (I):

in which A is an n+m valent linear or branched aliphatic C₁ to C₅₀radical, in which the carbon chain can be interrupted by O, S, —CO—O—,CO—NH, O—CO—NH or NH—CO—NH, an n+m valent aromatic C₆ to C₁₈ radical oran n+m valent cycloaliphatic or heterocyclic C₃ to C₁₈ radical, whereinthe radicals can carry one or more substituents, Y is not present, or isO, S, an ester, amide or urethane group, R¹ is hydrogen, an aliphatic C₁to C₂₀ alkyl or C₃ to C₈ cycloalkyl radical which can carry one or moresubstituents, R² is H, R³ is not present or is a C₁ to C₁₆ alkyleneradical which can be Ointerrupted by 0, HG is not present, or is —COOH,—P═O(OH)₂; —P═O(OH)(OR⁴); —O—P═O(OH)₂, —SO₂OH or —O—P═O(OH)(OR⁴), R⁴ isa C₁ to C₁₅ alkyl radical, phenyl or benzyl radical, n is a number from1 to 5 and m a number from 0 to 3, (b) 0 to 40 wt.-% diluent monomer,(c) 50 to 70 wt.-% cross-linker monomer, (d) 0.2 to 2.0 wt.-%polymerization initiator, (e) 20 to 50 wt.-% solvent, (f) 10 to 40 wt.-%adhesive monomer, and (g) 0 to 20 wt.-% nanofiller (filler with aprimary particle size of <50 nm).
 11. A dental filling materialcomprising: (a) 5 to 20 wt.-% acrylamide of the general Formula (I):

in which A is an n+m valent linear or branched aliphatic C₁ to C₅₀radical, in which the carbon chain can be interrupted by O, S, —CO—O—,CO—NH, O—CO—NH or NH—CO—NH, an n+m valent aromatic C₆ to C₁₈ radical oran n+m valent cycloaliphatic or heterocyclic C₃ to C₁₈ radical, whereinthe radicals can carry one or more substituents, Y is not present, or isO, S, an ester, amide or urethane group, R¹ is hydrogen, an aliphatic C₁to C₂₀ alkyl or C₃ to C₈ cycloalkyl radical which can carry one or moresubstituents, R² is H, R³ is not present or is a C₁ to C₁₆ alkyleneradical which can be interrupted by O, HG is not present, or is —COOH,—P═O(OH)₂; —P═O(OH)(OR⁴); —O—P═O(OH)₂, —SO₂OH or —O—P═O(OH)(OR⁴), R⁴ isa C₁ to C₁₅ alkyl radical, phenyl or benzyl radical, n is a number from1 to 5 and m a number from 0 to 3, (b) 0 to 30 wt.-% diluent monomer,(c) 0 to 30 wt.-% cross-linker monomer, (d) 0.2 to 2.0 wt.-%polymerization initiator, and (e) 50 to 80 wt.-% solvent.